CN102177090A - 硫化锂的制备 - Google Patents
硫化锂的制备 Download PDFInfo
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- CN102177090A CN102177090A CN2009801403670A CN200980140367A CN102177090A CN 102177090 A CN102177090 A CN 102177090A CN 2009801403670 A CN2009801403670 A CN 2009801403670A CN 200980140367 A CN200980140367 A CN 200980140367A CN 102177090 A CN102177090 A CN 102177090A
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- sulfide
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- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical compound [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title description 4
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 46
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 42
- 150000001875 compounds Chemical class 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 16
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims description 26
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 8
- 230000002829 reductive effect Effects 0.000 claims description 8
- 239000005864 Sulphur Substances 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 4
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 4
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 4
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-O oxonium Chemical compound [OH3+] XLYOFNOQVPJJNP-UHFFFAOYSA-O 0.000 claims description 4
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 claims description 3
- 229910052683 pyrite Inorganic materials 0.000 claims description 3
- 239000011028 pyrite Substances 0.000 claims description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 229910001508 alkali metal halide Inorganic materials 0.000 claims description 2
- 150000008045 alkali metal halides Chemical class 0.000 claims description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 2
- 239000003575 carbonaceous material Substances 0.000 claims description 2
- INPLXZPZQSLHBR-UHFFFAOYSA-N cobalt(2+);sulfide Chemical compound [S-2].[Co+2] INPLXZPZQSLHBR-UHFFFAOYSA-N 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 238000002407 reforming Methods 0.000 claims description 2
- 238000001149 thermolysis Methods 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 abstract 1
- 239000011593 sulfur Substances 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 7
- 229910001416 lithium ion Inorganic materials 0.000 description 7
- -1 LiMnPO 4 Inorganic materials 0.000 description 5
- 229910052976 metal sulfide Inorganic materials 0.000 description 5
- 230000001052 transient effect Effects 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 230000004907 flux Effects 0.000 description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 4
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 4
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical group [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 4
- 239000012429 reaction media Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 238000003780 insertion Methods 0.000 description 3
- 230000037431 insertion Effects 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 229910015645 LiMn Inorganic materials 0.000 description 2
- 229910021543 Nickel dioxide Inorganic materials 0.000 description 2
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- NFMAZVUSKIJEIH-UHFFFAOYSA-N bis(sulfanylidene)iron Chemical compound S=[Fe]=S NFMAZVUSKIJEIH-UHFFFAOYSA-N 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 2
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 2
- MRHPUNCYMXRSMA-UHFFFAOYSA-N nickel(2+) oxygen(2-) Chemical compound [O--].[O--].[Ni++] MRHPUNCYMXRSMA-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910011281 LiCoPO 4 Inorganic materials 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 229910013275 LiMPO Inorganic materials 0.000 description 1
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 1
- 229910013086 LiNiPO Inorganic materials 0.000 description 1
- 240000003936 Plumbago auriculata Species 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- PSHMSSXLYVAENJ-UHFFFAOYSA-N dilithium;[oxido(oxoboranyloxy)boranyl]oxy-oxoboranyloxyborinate Chemical compound [Li+].[Li+].O=BOB([O-])OB([O-])OB=O PSHMSSXLYVAENJ-UHFFFAOYSA-N 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 229910021450 lithium metal oxide Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000002816 nickel compounds Chemical class 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011833 salt mixture Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000010671 solid-state reaction Methods 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/20—Methods for preparing sulfides or polysulfides, in general
-
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- C01B17/24—Preparation by reduction
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- C01B17/26—Preparation by reduction with carbon
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- C01B17/24—Preparation by reduction
- C01B17/28—Preparation by reduction with reducing gases
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- C01D15/00—Lithium compounds
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Abstract
本发明提供一种用于制备硫化锂的合宜的工艺，该工艺涉及加热一种或多种含锂化合物和硫，其中该加热步骤在600℃至1500℃的温度下进行。
Description
本发明涉及硫化锂的制备。
锂离子电池是包括阳极(负极)、阴极(正极)和电解质材料的二次电池。它们通过锂离子在阳极和阴极之间的传递工作，并且它们不应当与锂电池混淆，锂电池的特性是含有金属锂。锂离子电池目前是最普遍使用的类型的可充电电池，并且通常，阳极包含插入材料，例如以焦炭或石墨的形式的碳。电活性电偶使用包含含锂的插入材料的阴极形成。典型的含锂的插入材料是氧化锂钴(LiCoO2)、氧化锂镍(LiNiO2)和氧化锂锰(LiMn2O4)。在其初始条件下，这种类型的电池是不带电的，因此为了递送电化学能，电池必须被充电以将锂从含锂的阴极传递到阳极。在放电时，锂离子被从阳极传递回阴极。在蓄电池的寿命期间，相继的充电和放电操作使锂离子来回地在阴极和阳极之间传递。由Tsutomu Ohzuku和Ralph Brodd在Journal of Power Sources 2007.06.154中提供了锂可充电电池的近期发展和可能的优点的综述。
令人遗憾地，氧化锂钴是相对昂贵的材料并且镍化合物难以合成。不仅如此，由氧化锂钴和氧化锂镍制成的阴极具有以下缺点：电池的充电容量显著地小于其理论容量。其原因是，少于1原子单位的锂参与电化学反应。此外，初始的容量在初始的充电操作期间被降低并且在每个充电循环期间更进一步降低。现有技术US 4,828,834试图通过使用主要由LiMn2O4组成的阴极来控制容量损失。另一方面，US 5910382描述了另一种途径，其使用混合有锂的金属材料，例如LiMPO4，其中M是至少一种第一排过渡金属。优选的化合物包括LiFePO4、LiMnPO4、LiCoPO4和LiNiPO4以及混合的过渡金属化合物，例如Li1-2xFe1-xTixPO4或Li1-2xFe1-xMnxPO4，其中0＜x＜1。
锂离子可充电电池的使用受到提供锂电极材料的高昂成本的限制，特别是对于氧化锂钴的情况。因此，目前的商业化被限制于高端应用，例如便携式计算机和移动电话。然而，将高度期望的是，进入更广阔的市场，例如电动车辆的供电，并且近年来一直在进行生产保持锂离子电池的高性能但同时使生产更便宜的材料的工作。为了实现该目标，已经提出，例如在JP Kokai第10208782号和Solid State Ionics 117(1999)273-276)中，硫化物可以用于代替氧化物作为阴极材料。虽然许多硫化物的使用得到对锂的相应的氧化物测量的较低的电压，但是某些基于硫化物的阴极的容量，以毫安小时每克测量，可以大至约3倍。基于此，某些基于硫化物的阴极在与它们的氧化物对应物(counterpart)比较时，在对锂金属阳极测量的蓄电池的阴极能量密度方面实现了约1.5倍的总优点，并且这使得这些硫化物的使用成为有吸引力的话题。例如，在锂铁硫化物的情况下，可以获得400mAhg-1的理论容量以及对锂金属阳极的2.2V的平均工作电压。
因此，含锂的过渡金属硫化物将是上文描述的锂金属氧化物的合宜的代替材料，且锂铁硫化物已经在专利文献中，例如在US 7018603中，被描述为二次电池中有用的阴极材料。含锂的过渡金属硫化物的商业化将很大程度上取决于它们的生产成本。以锂铁硫化物作为具体的实例，用于制备该材料的常规的工艺是通过固态反应，其中硫化锂(Li2S)和硫化亚铁(FeS)被密切地混合在一起并且在约800℃的温度下在惰性气氛下被加热。起始材料硫化亚铁(FeS)和二硫化铁(FeS2)是相对便宜的，因为它们作为天然存在的材料被发现并且被挖掘出地面。然而，反应过程的显著的缺点是，另一种起始材料Li2S不仅是昂贵的而且是对湿气高度敏感的。尤其是后一个问题明显意味着储存和处理起始材料的复杂性以及因此储存和处理起始材料的成本，尤其是对于大规模的商业化生产来说。此外，这种反应的动力学在US 7018603中被报导为是非常缓慢的并且可明显地需要长达一个月以完成反应，因此该路线被认为在能量成本方面是高度不利的并且对于电极材料的生产来说是商业上不可行的。
作为用于制备含锂的过渡金属硫化物的可选择的路线，US 7018603公开了使诸如FeS的过渡金属硫化物与硫化锂在高温(450℃至700℃的温度被举例说明)下在包含熔盐或熔盐混合物的反应介质中反应。优选的熔盐是卤化锂。虽然这种反应以良好的速率进行，但仍然存在使其不够理想的若干问题。首先，其使用Li2S作为起始材料的事实导致上文描述的处理和储存问题。第二，除了通过溶剂萃取之外，非常难以将反应介质(以1.5摩尔过量使用的熔融卤化锂)与期望的反应产物分离，并且这种类型的萃取是昂贵的。此外，即使在严格的提纯之后，在反应产物中仍然存在多至8％的反应介质盐，并且这种水平的杂质对于每克锂铁硫化物的充电容量是有害的。
考虑到生产硫化锂的费用，高度期望的是，找到简单的、高效节能的并且产生清洁产品的、用于硫化锂的生产的另外的可选择的路线。
因此，本发明提供了一种生产硫化锂的方法，该方法包括以下步骤：将一种或多种含锂化合物和硫在一起加热，其中该加热步骤在600℃至1500℃的温度下进行，并且进一步地其中含锂化合物选自以下物质中的一种或多种：氧化锂、碳酸锂、无水氢氧化锂、一水合氢氧化锂、草酸锂、硝酸锂以及在加热步骤期间是这些含锂化合物中的任一种的前驱体的任何材料。
加热步骤的温度不应当过高以致使硫从反应混合物损失，但是应高至足以使与一种或多种含锂化合物的反应发生。优选的温度在650℃至含锂化合物的分解温度的范围内。反应时间根据反应温度而变化，并且如人们可以预期的，温度越高则反应越快。
优选地，本发明的方法在非氧化性气氛和/或还原条件下进行，并且进一步优选地，还原条件由一种或多种还原气体和/或一种或多种还原剂来提供。一种或多种还原气体可以选自一氧化碳、氢气、转化气(氢气和氮气的混合物)、硫化氢、甲烷和其他气态烷烃，并且一种或多种还原剂可以选自碳和适合于在被加热时提供碳源的任何含碳材料。碳黑是优选的碳源。
可以生成的在本发明中使用的硫可以来源于硫华、黄铁矿(FeS2)、硫化钴(CoS2)和在热分解时生成硫的任何其他材料中的一种或多种。
在第二实施方案中，本发明提供了一种生产硫化锂的方法，该方法包括以下步骤：将一种或多种含锂化合物和黄铁矿在一起加热，其中该加热步骤在500℃至1500℃的温度下进行，并且进一步地其中含锂化合物选自以下物质中的一种或多种：氧化锂、碳酸锂、无水氢氧化锂、一水合氢氧化锂、草酸锂、硝酸锂以及在加热步骤期间是这些含锂化合物中的任一种的前驱体的任何材料。
合适的反应容器包括通常具有松配合盖(loose fitting lid)的玻璃碳或石墨坩埚，然而还可以使用密封的加压容器。对于工业规模生产来说，有利的是使用连续过程，例如旋转管式炉，但是还可以使用曲颈甑分批过程(retort batch process)。
本发明的反应中使用的含锂化合物优选在反应过程期间处于固态，这意指反应优选在不使用反应介质例如溶剂的情况下进行。有利地，反应物是首先使用球磨机来研磨以产生细粉末的固体材料，细粉末可以被直接使用或被首先压制为小球。
为了减少所形成的杂质的量并且为了优化反应条件，已经发现有利的是，向反应混合物中加入熔剂(flux agent)，熔剂也被称为矿化剂。熔剂或矿化剂在陶瓷工业中通常用于降低反应温度和缩短反应时间。诸如氯化钠、硼砂、氯化锂、氟化锂、氟化钠、硼酸锂和碳酸钠的矿化剂是已知的。本申请人已经发现，使用非常少量的矿化剂。可以使用任何碱金属卤化物，但是氯化锂和碘化锂是最优选的。可选择地，可以使用碳酸钠或氯化钠。发现在本发明中是有益的矿化剂的量是按重量计起始材料的1％至5％，优选按重量计1％至3％并且进一步优选按重量计起始材料的1％。
使用本发明的方法来固态制备硫化锂对于用于制备锂过渡金属硫化物来说是特别有利的。在将期望的过渡金属硫化物加入反应混合物中并且然后将其在600℃至1500℃的范围内、优选在700℃至1000℃的范围内的温度下加热之前，不需要分离由本发明的方法形成的硫化锂。与上文描述的现有技术方法不同，这种用于制备锂过渡金属硫化物的工艺不使用溶剂，因此该工艺明显地避免了与在反应过程结束时的溶剂除去相关联的问题。
Claims (8)
1.一种生产硫化锂的方法，包括以下步骤：将一种或多种含锂化合物和硫在一起加热，其中所述加热步骤在600℃至1500℃的温度下进行，并且进一步地其中所述含锂化合物选自以下物质中的一种或多种：氧化锂、碳酸锂、无水氢氧化锂、一水合氢氧化锂、草酸锂、硝酸锂以及在所述加热步骤期间是这些含锂化合物中的任一种的前驱体的任何材料。
2.根据权利要求1所述的生产硫化锂的方法，其中所述反应在非氧化性气氛和/或还原条件下进行。
3.根据权利要求2所述的生产硫化锂的方法，其中所述还原条件由一种或多种还原气体和/或一种或多种还原剂来提供。
4.根据权利要求3所述的生产硫化锂的方法，其中所述一种或多种还原气体选自一氧化碳、氢气、转化气(氢气和氮气的混合物)、硫化氢、甲烷和其他气态烷烃，并且所述一种或多种还原剂选自碳和适合于在被加热时提供碳源的任何含碳材料。
5.根据任一前述权利要求所述的生产硫化锂的方法，其中所述硫来源于硫华、黄铁矿、硫化钴和在热分解时生成硫的任何其他材料中的一种或多种。
6.一种生产硫化锂的方法，包括以下步骤：将一种或多种含锂化合物和黄铁矿在一起加热，其中所述加热步骤在600℃至1500℃的温度下进行，并且进一步地其中所述含锂化合物选自以下物质中的一种或多种：氧化锂、碳酸锂、无水氢氧化锂、一水合氢氧化锂、草酸锂、硝酸锂以及在所述加热步骤期间是这些含锂化合物中的任一种的前驱体的任何材料。
7.根据权利要求1至6中任一项所述的方法，还包括加入以按重量计起始材料的1％至5％的总量的一种或多种矿化剂。
8.根据权利要求7所述的方法，其中所述矿化剂包括碱金属卤化物。
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| CN117977044B (zh) * | 2024-04-01 | 2024-07-16 | 四川新能源汽车创新中心有限公司 | 一种硫化物基全固态电池物料的回收方法 |
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| WO2016119481A1 (zh) * | 2015-01-30 | 2016-08-04 | 浙江工业大学 | 一种硫化锂粉体的制备方法 |
| CN105016310A (zh) * | 2015-07-30 | 2015-11-04 | 广东先导稀材股份有限公司 | 一种高纯硫化锂的制备方法及装置 |
| CN110475745A (zh) * | 2017-02-03 | 2019-11-19 | 雅宝德国有限责任公司 | 高反应性、无尘且自由流动的硫化锂及其制备方法 |
| CN110475745B (zh) * | 2017-02-03 | 2023-03-31 | 雅宝德国有限责任公司 | 高反应性、无尘且自由流动的硫化锂及其制备方法 |
| CN108400327A (zh) * | 2018-01-11 | 2018-08-14 | 北京天工新材科技发展有限公司 | 一种硫化锂的制备方法 |
| CN110526219A (zh) * | 2019-08-26 | 2019-12-03 | 浙江工业大学 | 一种硫化锂粉体的合成方法 |
| CN110790239A (zh) * | 2019-08-26 | 2020-02-14 | 浙江工业大学 | 一种硫化锂粉体的机械球磨合成方法 |
| CN110790239B (zh) * | 2019-08-26 | 2022-01-28 | 浙江工业大学 | 一种硫化锂粉体的机械球磨合成方法 |
| CN112520763A (zh) * | 2020-08-03 | 2021-03-19 | 浙江工业大学 | 一种利用硫酸锂制备硫化锂的方法 |
| CN112520763B (zh) * | 2020-08-03 | 2022-04-15 | 浙江工业大学 | 一种利用硫酸锂制备硫化锂的方法 |
| CN113401878A (zh) * | 2021-06-16 | 2021-09-17 | 高能时代(佛山)新能源科技有限公司 | 一种硫化锂的制备方法 |
| CN116969422A (zh) * | 2023-07-31 | 2023-10-31 | 武汉中科先进材料科技有限公司 | 一种硫化锂的制备方法、硫化物固态电解质及全固态电池 |
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